Process for dyeing nitrogenous fibers



United States Patent 3,697,940 PROCESS FOR DYEING NITROGENOUS FIBER S Richard Casty, Kaiseraugst, Switzerland, assignor to Cuba Company, Inc., Falr Lawn, NJ. No Drawing. Filed Feb. 1, 1960, Ser. No. 5,634 Claims priority, application Switzerland Feb. 19, 1959 16 Claims. (Cl. 8-54) It is known that wool can be advantageously dyed with sulfonated copper phthalocyanines in the presence of a polyglyool ether containing a basic nitrogen atom; without addition the resulting dyeings are as a rule uneven and practically useless. A similar behavior is observed in the case of other dyestufis containing sulfonic acid groups, for example those which contain at least two sulfonic acid groups and are capable of entering a chemical bond with the fiber, or the 1:2-chromium or 1:2-cobalt complexes of azo dyestulfs which contains sulfonic acid groups. The advantageous effect of the nitrogenous assistants is, however, in general the less pronounced, the lighter the tint. More especially in the case 7 of the socalled pastel tints even in the presence of the afore-mentioned assistants the dyeings obtained are skittery and the textile materials are not dyed right through. Furthermore, it is as a rule necessary to raise the temperature of the dyebath from about 50 C. to the boil slowly and evenly; this is necessary to ensure that the material is dyed evenly and right through, both in the case of light and dark shades.

The present process enables these disadvantages to be overcome substantially or even completely. According to this process nitrogenous fibers are dyed with dyestulis containing at least 2 groups imparting solubility in water, preferably sulfonic acid groups and in the presence of a compound containing at least one basic nitrogen atom to which is attached at least one radial containing a polyglycol ether chain, and the molecule contains at least three as well as at least 4 carbon atoms not forming part of such a group, the dyeing being performed in the presence of an anion-active compound that has no dyestufl' character but possesses alfinity for the nitrogenous fibers.

The present process is suitable for dyeing nitrogenous fibers that can be dyed with acid dyestuffs by the conventional methods, for example silk, polyamide fibers of e-caprolactam or of adipic acid and hexamethylenediamine. The process is especially suitable for dyeing wool, or if desired wool blended with other fibers which, if desired, may likewise contain nitrogen.

The present process can be carried out with any dyestufi that contains at least two groups imparting solubility in water, for instance carboxyl groups or preferably sulfonic acid groups and is suitable for dyeing nitrogenous fibers, more especially with dyestuffs that are conventionally used for dyeing wool from an acetic acid bath, including those of the following types:

(A) Dyestufi's that contain sulfonic acid groups and are gapable of entering a chemical bond with hydroxylated bers.

(B) Sulfonated copper phthalocyanines.

(C) Dyestuffs that consist substantially of 1:2-chromium or l:2-cobalt complexes of azo dyestuffs and contain groups imparting solubility in water.

3,097,040 Patented July 9, 1963 ICC of dyestuffs, being, for example, stilbene, perinone, peridicarboxylic acid imide, nitro, triphenylmethane, phthalocyanine dyestutfs or, above all acid, .anthraquinonc or azo dyestulis including both metal-free and metalllferous and metallizable monoazo and polyazo dyestulis that contain a grouping or substituent that is capable of reacting with the nitrogenous fibers. In general, particularly good results are obtained with dyestuffs containing two or more sulfonic acid groups.

Among the above reactive groups and substituents there may be mentioned, for example, the ethylene imlde group, epoxide groups, the vinyl grouping in a vinylsultone group or in the acrylic acid radical, and above all, labile substituents that are easy to eliminate with entrainment of the bond electron pair.

As labile substituents capable of elimination with entrainment of the bond electron pair there may be mentioned, for example, aliphatically bound phosphoric or sulfuric acid ester groups, sulfonic acid fluoride groups, aliphatioally bound sulfonyloxy groups and above all halogen atoms, more especially a mobile chlorine atom. These labile substituents are advantageously in the 7- or ,S-position of an aliphatic radical which is bound to the dyestuli molecule directly or through an amino, sulfone or sulfonamide group. Suitable groups are, for exam- 7 ple, those of the composition these groups may be bifunctional in that, on one hand, they render the dyestufi soluble in water and, on the other, they are capable of reacting with the fibrous material.

In those dyestuifs suitable for the'present process which contain as labile substituents halogen atoms, these mobile halogen atoms may also be contained in an aliphatic acyl radical (for example in the fi-poei-tion of a propionyl radical) or preferably in a heterocyclic system, and in the last-mentioned case there are suitable dyestufis con-- taining a monohalogen-ated heterocyclic group, for example a monochlorinated 1:3:5-triazine radical such as the 1:3 :5triazine radical of the formula N-Gl in which X represents an alkyl, aryl, aralkyl, alkylmercapto or arylmercapto group or more especially an unsubstituted or substituted amino group or a, preferably substituted, hydroxyl group-as well as dyestulfs containing a dichlorotriazine group or a trichloropyrimidine or dichloropyrimidine radical.

Numerous dyestulfs of the specified kind are known or can be manufactured by known methods, for example from dyestutl components that as such contain the aforementioned labile substituents, or by incorporating such a labile substituent or a radical containing such a labile substitutent by a known method in the dyestulf molecule of a previously prepared dyestufi'. In this manner, by reacting an azo or anthraquinone dyestufr" containing a reactive hydroxyl, mercapto or above all amino group, for example with chloracetyl chloride, with fi-bromopropionyl chloride or fi-chloropropionyl chloride or chloropropionic anhydride, with cyanuric chloride or with a primary condensation product of cyanuric chloride containing two chlorine atoms and, instead of the third chlorine atom of cyanuric chloride, an organic radical, there are obtained valuable condensation products that still contain a mobile chlorine atom and are suitable for dye- 3 ing by the present process. Dyestuffs suitable for use in the present process that contain a sulfonylated hydroxyl group can be prepared, for example, by reacting 1 molecular proportion of a dyestufi containing an alkoxy group,

4 (c), (d) and (e), the dyestuffs F and F may in all cases be of identical or different constitution. The groups imparting solubility in water may take up any desired position in the dyestuffs F and F they may be present in for example a sulfonic acid-N-hydroxyalkylamide group, the radical of the diazo component or of the coupling or a fl-hydroxyalkylsulfonic acid with at least 1 molecular component, and if desired, 2, 3 or 4 such groups maybe proportion of an organic sulfonyl halide, for example present in one and the same radical. As a rule, excessive para-toluenesulfonyl chloride, benzenesulfonyl chloride massing of solubilizing groups, more especially sulfonic or ethanesulfonyl chloride, or with concentrated sulfuric acid gto11p8- above all in compounds of a relatively low acid or with chlorosulfonic acid, in a manner such that molecular Weight-15 undesirable 136631186 thlS may reduce the hydroxyl group is acylated. the wet fastness of the dyeings. It has been found par- As dyestuffs of the kind defined above under (B) there tlculafly adVflmflgeu$ W11e n wmplex contains, for are to be used in the present process sulfonated copper p 2 t0 4 SillfOIllc field E P phthalocyanines that contain, for example 2, 3 or 4 sulh g p (zapflble 0f formlllg mfital P P fonic acid groups and, if desired, further substituents 15 i In the mOIlOflZO flyfitllfls are Pmferably such as halogen atoms, more especially chlorine atoms, or dIhYdYOXYflZO g p g Y Y- Q Y- sulfonamide groups. There are also suitable dyestuff 3Z0 grouPlngs, though also other complex-formlflg P mixtures, for example sulfonation mixtures the constitare admlsslble, Such orthojhydfloxy'ortho Y- uents of which differ as to the number of sulfonic acid i' oriho-llldmxy-oftho 'ammofllo f l f g groups present in them, or mixtures of sulfonated copper j fi 1150 sultable further dyestuffs wmamms P phthalocyanines with other dyestuffs suitable for dyeing fomc 391d gmupsr not by tha above defimnon nitrogenous fibers from an acidic dyebath, among them, (A), (B) (C), Preferably and anthraqumone above all, those defined under (A) and (C) above, stuffs of which a large variety has been used for a long The dyestuffs defined under (C) are above all 1:2- P Y chromium or cobalt complexes of azo dyestuffs, more esperhB a ntl ned nitrogenous compounds contain cially monoazo dyestuffs, that is to say complexes in which at least one bflslc f atom to which 15 attafihed two molecular proportions of an am d t fi or 1 melee, least one radical containing a glycol ether chain; this Pmpmflon each of two different azo dyestuffs are chain consists of at least two members of the formula bound in complex union to one atom of chromium or J l cobalt. The complex may, for example, contain one f glif ig :53P i g gi i ggzgggg i;i f and it can be connectedto the nitrogen atom either di- Suitable solubilizing groups are also in this case free cari or through a budge m for examp 1e an boxyl groups or more especially free a] ylene group, such as the radical of the formula sulfonic acid groups (SO -cation however a earboxyl CH CH CH group pqmclpatmg m the forfnatlori of the i 1S The molecule of the nitrogen compound should contain not considered to be a group imparting solubility in waat least three groups of me formula ter since, in this kind of bond, it is no longer capable of imparting solubility in water. The groups imparting solubility in water may occupy any desired position in the 40 complex. {\s a rule, it is of advantage when at least one p -efgrably three groups f the f l sulfomc acid group is present. When the complex contains a total of two groups imparting solubility in water, CHT CHT O and when the complex-forming metal is represented by Furthermore, the nitrogen compound must contain at Me and the two dyestuffs by F and F respectively, the least 4 carbon atoms not forming part of such a group. following possibilities exist which are shown in the follow- Inter alia, it preferably contains also at least one aliphatic ing schematic table: or alicyclic radical with at least 8 carbon atoms, preferz ooofi 1-00 0H+1SOaH 2-SO3H 000E COOH 50311 F1 F1 Fl I dye oontalns 2 solublllzlng groups, I dye is free from (a) Mo OOOH (e) Me S0 11 (e) Me SOQH such groups.

F g F l F2 Fr-COOH F|CO0H F|-SO3H Both dyes contain 1 solublllzing group each (b) Me (d) Me (U Me Fn-COOH Fz-S0 H -803E Especially valuable--inter alia because of their ready aoably an aliphatic radical with a chain of at least 12 carbon cessibility-are the dyestuffs covered by the above Foratoms, or an aromatic radical with an aliphatic side chain, mulae (e) and (j) which contain two sulfonic acid groups which is bound to the basic nitrogen atom through an in the molecule of the dyestuff complex, or quite genaryl carbon atom. erally dyestuffs containing at least two sulfonic acid From the foregoing it will be realised that the present groups in the molecule of the complex, and among them, process can be advantageously performed with the use above all, dyestuffs in which-as is the case with the comas nitrogenous compound of the kind referred to above plexes (f)--two monoazo dyestuif molecules, each of which contains at least one sulfonic acid group, are bound in complex union to one atom of chromium or cobalt.

Apart from the difference between F and F which of a reaction product of at least 3 molecular proportions of an azfi-alkylene oxide with 1 molecular proportion of an organic compound containing at least one basic primary or secondary amino group, or one basic tertiary exists as a matter of course between the compounds (a), amino group and in addition an alcoholic hydroxyl group,

or of a salt thereof or of a quaternary ammonium salt derived therefrom.

Products suitable for use in the present process are those which are accessible by reacting 1 molecular proportion of an amine with at least 3, for example 3 to 20, molecular proportions of an alkylene oxide, for example a product obtained by reacting: 1 mol of dodecylamine with about 6 mols of ethylene oxide, or 1 mol of oleylamine with 6, 8 or 16 mols of ethylene oxide, or 1 mol of stearlyamine with 4, 8 or 16 mols of ethylene oxide, or monoalkyl-propylenediamine, whose alkyl radical corre sponds to the radical of the tallow fatty acids, with 8 mols of ethylene oxide, or monoalkyl-propylenediamine, whose alkyl radical is unbranched and contains 16 to 18 carbon atoms, with 6 mols of ethylene oxide.

From the foregoing it will be realized that nitrogen compounds of the formula OI-E N are particularly suitable for use in the present process; in this formula R represents a preferably unbranched aliphatic hydrocarbon radical containing at least 12, and preferably 16 to 22, carbon atoms; m and :1 each 1 or 2, and p, q and r represent whole numbers, the sum p+q+ (m-1)(rl) being at least 3 and at most 20, at least one of the symbols p, q or m-l being a number greater than 1.

It will further be realized that nitrogen compounds of the formula are particularly suitable for performing the present process; in this formula R represents a preferably unbranched aliphatic hydrocarbon radical with at least 12 and preferably 16 to 22 carbon atoms, and p and q represent whole numbers, the sum p+q being at least 3 and preferably from 8 to 16 inclusive.

Instead of a compound containing free alkoxy groups there may be used as assistants in the present process acid esters of polybasic acids, for example those of phosphoric or sulfuric acid derived from said alkoxy compounds, or the water-soluble salts of these esters, for example salts of alkali metals, ammonia or an amine.

The dyeing according to the present process is performed in the presence of an anion-active compound that has no dyestulf character but possesses affinity for the nitrogenous fibers. It is of advantage to use a compound containing sulfonic acid groups in which said groups are advantageously attached to aromatic nuclei, such as benzene nuclei or more especially naphthalene nuclei.

As examples of suitable compounds may be mentioned:

Alkali metal sulfonates of benzene hydrocarbons having a long aliphatic chain,

Alkali metal monosulfates of 2-alkylbenzimidazoles containing a higher alkyl radical, for example the sodium salt of the monosulfonated Z-heptadecyl-N-methylbenzimidazole,

Alkali metal sulfonates of naphthalene substituted by lower alkyl groups, for example sodium diisobutylnaphthalenesulfonate,

Sulfonated condensation products of oxyaryl compounds of the benzene series with formaldehyde, more especially those obtained by condensing an hydroxyaryl compound of the benzene series with formaldehyde, followed by sulfonation and a secondary condensation of the sulfonated product with formaldehyde;

especially good results are obtained with reaction products of naphthalenesulfonic acids with formaldehyde.

Further suitable are products of a different kind, for

example fiber-afiinic anti-moth preparation containing sulfonic acid groups, or so-called Wool resist agents (immunizing agents) of the kind obtained by reacting a phenol or thiophenol with an alkali metal sulfide or sulfite or sulfite-formaldehyde. The amounts of substances to be added to the dyebath used in the present process may vary Within relatively wide limits. The amount of dyestulf depends, of course, on the desired tinctorial strength. It is advantageous to adapt the amount of nitrogenous compound to the amount of dyestuff so that they are used at a ratio of about 1:8 to 1:2; it is of advantage to add the nitrogen compound in an amount equal to about of the amount of dyestulf. At any rate, even when a light shade is aimed at-for which less than 1% of dyestuif calculated on the weight of the fibers is used-the nitrogen compound should be at least 0.25% of the weight of the fibrous material.

The amount of fiber-afiinic anion-active compound is advantageously made the greater, the less dyestuff is used. For very pale shades, for which 0.1% of dyestulf or even less and about 0.5% of the nitrogenous compound is used, it may be advantageous to add about 0.3 to 1% of the anion-active compound.

It is further possible to manufacture a preparation containing the nitrogenous compound and the anion-active substance. Such a stable preparation suitable for performing the present process contains (a) A compound containing at least one basic nitrogen atom to which is attached at least one radical containing a polyglycol ether chain, the molecule containing at least three groups of the formula and at least 4 carbon atoms not forming part of such a group, and

(b) An anion-active substance that has no dyestufi" character but possesses alfinity for the nitrogenous fiber. In this case there are used for every part of the nitrogenous compound advantageously 0.2 to 2 parts of the anion-active compound and, if desired, a certain amount of water is added to obtain such a preparation in the form of a mixture or solution.

The amount of such a preparation to be used is such as to ensure the presence of about /2 to 2% of the two assistants (taken as a whole and calculated on the weight of the fibrous material) in the dyebath.

Furthermore, it is found advantageous to dye in a weakly acidic medium so that the pH value of the dyebath is about 3 to 6, preferably 4 to 5. This pH value is advantageously adjusted by adding acetic acid, or if desired, formic or sulfuric acid. It is of further advantage to add sodium sulfate to the dyebath. In some cases it is advantageous to adjust the desired acidity of the dyebath by adding an ammonium salt capable of giving off acid, for example ammonium sulfate, phosphate or acetate.

As is conventional in dyeing nitrogenous fibers, more especially wool, the dyeing is performed at an elevated temperature, advantageously by beginning the actual dyeing operation at about 50 to C., then raising the dyebath to the boil, and continuing and finally terminating the operation at the boil. However, it has been observed that even when dyeing wool by the present process it is not at all necessary to raise the temperature close or exactly to the boiling point of the dyebath; as a rule, practically identical results are obtained by conducting the dyeing operation well below the boiling temperature, for example within a temperature range of 80 to C. Furthermore, it has surprisingly been observed that it is of advantage to pretreat the fibrous material to be dyed, more especially the wool, in a bath containing at first all ingredients except the dy-estufl, that is to say the nitrogenous polyglycol compound, the fiber-afiinic anion-active 7 8 substance and acid or an ammonium salt. The textile When the afore-rnentioned assistants are omitted, an unmaterial is pretreated in this bath at 80 to 100 C. for even, practically useless dyeing results. to minutes. Then-in general without cooling- A level dyeing is likewise obtained by the above process the dyestuff is added in the form of an aqueous solution, with the only modification that, after addition of the and the material is dyed at to 100 C. until the dyedyestuff solution, the dyebath is raised to C. instead bath is practically exhausted. of to the boil, and dyeing is then conducted and completed By increasing the pH value of the acidic bath after the at about 85 C.

dyestuff has been absorbed by the material, the wet fast- Furthermore, instead of adding to the dyebath sucness of the latter to migration of the dyestulr' can be cessively the ethylene oxide adduct and the reaction proclimproved. 10 not of naphthalenesulfonic acid, there may be added to Unless otherwise indicated, parts and percentages in the it 1 part of a preparation obtained by mixing 1 part each following examples are by weight. of the two afore-mentioned assistants with 1 part of water. EXAMPLE 1 mz'lInhleesthylene oxide adduct is prepared in the following parts of knitting wool, 3000 parts of water, 10 15 100 parts of commercial oleylarnine are mixed with 1 parts of crystalline Sodium Sulfate, 6 parts of acetic acid part of finely distributed sodium and heated to 140 C., of 40% strength and 0.5 part of the adduct described whereupon ethylene oxide is introduced at 135140 C. below of oleylamine and ethylene oxide, 30 parts of When the ethylene oxide is being absorbed rapidly, the crystalline sodium sulfate and 0.6 part of a reaction prodreaction temperature is lowered to -125 C., and the not of naphthalenesulfonic acid and formaldehyde are introduction of ethylene oxide is continued until 113 heated to 80 C. A solution of 0.1 part of the dyestufi 20 parts thereof have been absorbed. The resulting reaction of the formula product gives a practically clear solution in water.

4 S0311 H0 21 OH 3CONH- :N-

HOaS- NH-C -NH- in a little water is added to the dyebath prepared in this Instead of with the dyestufi of the Formula 4 wool can manner. In the course of /2 hour the bath is raised to 35 be dyed in the manner described above with each of the the boil and the wool is dyed for 1 hour at the boil, then following dyestuffs, whereby level dyeings are likewise rinsed and dried. A light-red, very pure tint is obtained. obtained:

(5) -N=N (potassium salt) Yellow.

2 l 113E NH-CHz-C Ha-O-SO r-OH N S 0 311 HO NH--G l l l N (e) HiCON=N Hots so.n n

N H0 I (7) 01-0 0 HN S 03H Yellow.

H l o-N 80311 HO N Red.

\ I (8) S 0 11 Blue:

H03 HN- 0 C -01 l i 03H 0 Copper phthnlocyanine-disulfonic acid containing 1 t 2 S0a'NH'CHzCHaCl groups Blue. Copper phthalocyanine further substituted by two sulfonic acid groups and 2 groups of the formula Turquoise.

O NH-CH OSO:-OH; those substituents are in positions 3, 4', 4", and 4". Copper phthalooyonine-dlsultonic acid containing 2 3 groups of the iorniula Do.

N -S01NHGHz-CHa-NH-(l1 (l-EN- EXAMPLE 2 ample 1 of oleylamine and ethylene oxide, 0.4 part of a 100 parts of hard-twisted Woolen yarn are dyed in a dyebath containing: 3000 parts of water, 30 parts of crystalline sodium sulfate, 4 parts of acetic acid of 40% strength, 0.5 part of the ethylene oxide adduct described in Example 1, 0.5 part of a condensation product of naphthalene-sulfonic acid and formaldehyde, and 0.2 part of copper phthalocyanine-trisulfonic acid.

The yarn is immersed in the dyebath at about 50 C. which is then raised to and maintained at 85 C. for 30 minutes, then further raised to the boil, and dyeing at the boil is performed for 30 minutes.

A pale, greenish blue, level dyeing is obtained.

EXAMPLE 3 The method described in Example 2 is used with the following modification:

The sodium sulfate is omitted, and there are used 0.5 part of the ethylene oxide adduct, 0.2 part of the reaction product of naphthalenesulfonic acid and formaldehyde, and 0.75 part of the afore-mentioned dyestuif.

A very level turquoise dyeing is obtained. The hardtwisted yarn is dyed right through.

EXAMPLE 4 A dyebath is prepared from 3000 parts of water, parts of crystalline sodium sulfate, 6 parts of acetic acid of 40% strength, 0.5 part of the adduct described in Excondensation product of naphthalenesulfonic acid and formaldehyde, and 0.2 part of the dyestutf described below. At to C. parts of knitting wool are immersed in this dyebath, which is then raised to the boil within /2 hour, and dyeing is performed for 1 hour at the boil. The dyed wool is rinsed and dried. A level, pale, bluish grey dyeing results.

Manufacture of the Dyestufl 41.6 parts of the monoazo dyestuff obtained by coupling diazotised l-amino-2-hydroxynaphthalene-4-sulfonic acid with l-hydroxynaphthalene are dissolved in 1000 parts of water and treated with 100 parts by volume of a sodium chromesalicylate solution containing 2.85% of chromium. The whole is refluxed for several hours, whereupon the metallization is complete. The chromium complex is salted out with sodium chloride, filtered off and dried.

EXAMPLE 5 The procedure used is the same as that described in Example 4, except that the chromiferous dyestutf used in that example is replaced by one of the undermentioned 1:2-metal complexes which are accessible by the usual methods, and level dyeings are likewise obtained.

In the Table A are shown 1:2-complexe in which two molecular proportions of a dyestuif are bound in complex union to one atomic proportion of metal.

TABLE A.

Metal Dyestufl Tint HO OH I i C-CH C0...- 3) 0:5- N= -C\ Brown:

OzN Ho|s OIH (|)H O0..." (19) --N=N Vioiettish brown. 1110, HaC-GCHI B015 OH l CN- SO\H Cr-..- (20) N=NC Red.

C=N G1 H C (|)H IiO Cr. (21) HOQS N=N Reddlsh blue.

TABLE A-Continued.

Metal Dyostufl Tint 021? 0TH H? Cr... 22 N=N Reddish blue.

021? OH HzN G0... (23) N=N Green.

OZN

HOaS

H03? (|)H HO C0 24 ON: Violet.

SOQH

OH HOaS OH I l C-NH Co (25) QN=NC Reddish brown.

1 C=N c1 1 In the following Table B are listed til-complexes in bound to one atomic proportion of metal in complex which 1 molecule each of two different dyestulfs are union.

TABLE B Metal 1st dyeszufl 21d dyestufl Tim;

(!)H H0 503B H03? m H0 C] c: H0aS N=N ON=N Blue.

7) Cl 2 a or HOaS-8 =N-8 H0=s- N Grey-blue.

21 2s) 01 ?H 13,1 H01? 0H H(|) 31 Cr 0zN-O =N -N=N Bluish grey.

80:11 Cl 01 H(|) 110.? ()H Hf!) (31 Cr Hols N=N N=N Do.

i OzN 1 TABLE 13-Continucd Metal 1st dyestuff 2nd dyestufl Tint HO OH HO H018 OH l l l C -01 Brown.

Cr HO S -N=N N=NO I 1: (MN l OzN HO H 0:8 OH H O HO S O H l l l I C--N C 0 011 Brown violet.

Cr -N=N N=N--C C=N OaN G1 ()H HOi St 0 H ()H H? (Ill 01' H03S -N=N- N=N- Grey blue.

I OlN Cl EXAMPLE 6 A dyebath is prepared from 3000 parts of water, parts of ammonium phosphate, 0.6 part of the adduct described in Example 1 of oleylamine and ethylene oxide, as well as 0.4 part of a condensation product of naphthalene-sulfonic acid and formaldehyde, and 100 part of a woollen fabric are immersed in it. The whole is raised to the boil within a short time and maintained at the boil for 15 to minutes. An aqueous solution of 2 pants of one of the dye stuffs described in Examples 4 and 5 is then added to the boiling dyebath, and dyeing is performed for 1 hour at the boil.

Fast, level dyeings result of a darker tint than those produced as described in Examples 4 and 5.

EXAMPLE 7 Dyeing is performed as described in Example 4 or 5, except that the dyebath is raised to C. instead of to the boil. Level dyeings are likewise obtained.

EXAMPLE 8 A dyebath is prepared from 3000 parts of water, 5 parts of acetic acid of 40% strength, 0.5 part of the ethylene oxide adduct described in Example 1, 0.6 part of a condensation product of naphthalenesulfonic acid and formaldehycle, and 0.1 part of one of the following dystuffs. At 50 C. parts of wool gabardine are immersed in the dyebath, the temperature is raised Within /2 hour to the boil, and dyeing is performed for 1 hour at the boil. The fabric is dyed a level tint right through.

H O HN-O C (as C -N=N Ruby red.

H O s S 0 1H H C l C H: C H

I I o H O as H O 35- S 0 3H i i (42) -S 0 E H O as- Blue.

17 EXAMPLE 9 A dyebath is prepared from 3000 parts of water, parts of crystalline sodium sulfate, 6 parts of acetic acid of 40% strength, 0.5 part of one of the undermentioned ethylene oxide adducts (a) to (g), 0.4 part of a condensation product of naphthalcnesulfonic acid and formaldehyde, and 0.2 part of one of the dyestuifs of the tFormulae 4, 21 or 30. At 50 C. 100 parts of knitting wool are immersed in the dyebath, which is then raised within /2 hour to the boil, and the wool is dyed for 1 hour at the boil, then rinsed and dried. Level dyeings result in all cases.

(a) Adduct of 8 molecular proportions of ethylene oxide and a mixture of arachidylamine and behenylamine. (b) Adduct of 12 molecular proportions of ethylene oxide and a mixture of arachidylamine and behenylamine. (c) Adduct of 4 molecular proportions of ethylene oxide and stearylamine.

(d) Adduct of molecular portions of ethylene oxide and a mixture of arachidylamine and behenylamine. (e) Adduct of 8 molecular proportions of ethylene oxide and a mixture containing 30% of palmitylamine, 45%

of octadecenylamine and of stearylamine.

(f) Adduct of 6 molecular proportions of ethylene oxide and a mixture of N-alkyl-propylenediamines of which the alkyl residues contain 16 to 18 carbon atoms.

(g) Adduct of 8 molecular proportions of ethylene oxide and a mixture of N-alkyl-propylenediamines of which the alkyl residues contain 16 to 18 carbon atoms.

EXAMPLE 10 The method described in Example 4 is used, except that the condensation product of naphthalenesulfonic acid and formaldehyde is replaced by the product that is obtained when a mixture of 2 molecular proportions of phenol and 1 molecular proportion of paradodecylphenol is condensed with 1.75 molecular proportions of formaldehyde, the reaction product is sulfonated, the sulfonic acid thus obtained is further condensed with formaldehyde, and the product is neutralised with ammonia. A level dyeing is obtained.

I nstead of the assistant prepared from phenol and paradodecylphenol there may be used a product obtained from 2 molecular porportions of phenol and 1 molecular proportion of paracresol or para-octylphenol.

What is claimed is:

l. A process which comprises dyeing wool with dyestuffs containing at least 2 fiO S-groups in the presence of a compound of the formula L j... J

PC r-O)ri-H m: in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms, m and it each represent a whole number of at the most 2, and p, q and r represent whole numbers, the sum p+q+(ml)(r-l) being at least 3, at least one of the symbols p, q and (r-l) being greater than 1, and in the presence of an anion-active substance that has no dyestutf character but possesses afiinity for the Wool.

2. A process which comprises dyeing wool with dyestuffs containing at least 2 groups imparting solubility in water in the presence of a compound of the formula (-C Hz-CH:O) 9-H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p+q being at least 3 and at most 20, and in the presence of an anion-active substance that has no dyestutf character but possesses atfinity for the wool.

3. A process which comprises dyeing wool with dyestuffs containing at least 2 HO S-groups in the presence of a compound of the formula (CH3-CHO) p' H RN/ (cH,-0H,-o-J.,-H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p+q being at least 3 and at most 20, and in the presence of an anion-active substance that has no dyestutf character but possesses affinity for the wool.

4. A process which comprises dyeing wool with dyestuffs containing at least 2 HO S-groups in the presence of a compound of the formula (CHt0H-0-).,H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p-I-q being at least 3 and at most 20, and in the presence of a sulfonated condensation product of a hydroxybenzene and formaldehyde.

5. A process which comprises dyeing wool with dyestuffs containing at least 2 Ho -groups in the presence of a compound of the formula (oHtoHt o-),,H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p+q being at least 3 and at most 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

6. A process which comprises dyeing wool with dyestuffs containing at least two sulfonic acid groups and which are capable of entering a chemical bond with hydroxylated fibers in the presence of a compound of the formula (CH:GH:0-) -H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p-l-q being at least 3 and at most 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

7. A process which comprises dyeing wool with dyestuffs containing at least two sulfonic acid groups and at least one chlorotriazine radical in the presence of a compound of the formula a Hr-0) H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p+q being at least 3 and at most 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

8. A process which comprises dyeing wool with copperphthalocyanines containing at least 2 sulfonic acid groups in the presence of a compound of the formula -cn,-cHt-o ),.-H

( C C 2- O) u H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p|-q being at least 3 and at most 19 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

9. A process which comprises dyeing wool with 1:2- chromium complexes of azo dyestuffs, the molecule of the chromium complex containing at least two sulfonic acid groups in the presence of a compound of the formula (CH -GH=-O-) -H in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p-l-q being at least 3 and at most 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

10. A process which comprises dyeing wool with 1:2- cobalt complexes of azo dyestuffs, the molecule of the cobalt complex containing at least two sulfonic acid groups in the presence of a compound of the formula (C1IzCHgO-) -I'I R-N\ (CH1-OHIO-)QH in which R represents an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and p and q represent whole numbers, the sum p+q being at least 3 and at most 20, and in the presence of a condensation product of naphthalene sulfonic acid and formaldehyde.

11. A stable preparation containing (a) a compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms, m and n each represent a whole number of at the most 2, and p, q and r represent whole numbers, the sum p+q+(m1)(r-1) being at least 3, at least one of the symbols p, q and (r-l) being greater than 1, and (b) an anion active substance that has no dyestuff character but, possesses aflinity for nitrogenous fibers. 12. A process which comprises dyeing wool with metalfree azo dyestulr' containing in its molecular structure at least 2 HO S-groups in the presence of (a) a compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms; each of m and n represents a whole number of at most 2; and each of p, q and r represents a whole number, the sum p+q+(m-l)(rl) being at least 3, at least one of the symbols p, q and (r-1) being greater than 1', and (b) an anion-active substance that has no dyestuff character but possesses aflinity for wool.

13. A process which comprises dyeing wool with phthalocyanine dyestuif containing in its molecular structure at least 2 HO S-groups in the presence of (a) a com pound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms; each 20 of m and n represents a whole number, the sum p+q+(m-1)(r-1) being at least 3, at least one of the symbols p, q and (r-1) being greater than 1; and (b) an anion-active substance that has no dyestutf character but possesses atfinity for wool.

14. A process which comprises dyeing wool with 1:2- rnetal complex dyestutf containing in its molecular structure at least 2 HO S-groups in the presence of (a) a compound of the formula HrCHr O/Pl H in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms; each of m and n represents a whole number of at most 2; and each of p, q and r represents a whole number, the sum p+q+(m-1)(r1) being at least 3, at least one of the symbols p, q and (r--1) being greater than 1; and (b) an anion-active substance that has no dyestuff character but possesses affinity for wool.

15. A process which comprises dyeing wool with anthraquinone dyestuir" containing in its molecular structure at least 2 HO s-groups in the presence of (a) a compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms; each of m and n represents a whole number of at most 2; and each of p, q and r represents a whole number, the sum p|q+(m1)(r1) being at least 3, at least one of the symbols p, q and (r-l) being greater than 1; and (b) an anion-active substance that has no dyestutf character but possesses atfinity for wool.

16. A process which comprises dyeing wool with fiberreactive anthraquinone dyestutf containing in its molecular structure more than 2 Ho s-groups in the presence of (a) a compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at most 22 carbon atoms, each of m and n represents a whole number of at most 2', and each of p, q and r represents a whole number, the sum p+q+(ml)(r1) being at last 3, at least one of the symbols p, q and (r-1) being greater than 1; and (b) an anion-active substance that has no dyestuff character but possesses affinity for W001.

References Cited in the file of this patent UNITED STATES PATENTS 1,926,556 Nuesslein Sept. 12, 1933 1,970,578 Schoeller et al Aug. 21, 1934 2,179,371 Dyer Nov. 7, 1939 2,214,067 Petersen Sept. 10, 1940 2,228,369 Schoeller Jan. 14, 1941 2,310,074 Gotte Feb. 2, 1943 2,773,871 Brassell et a1. Dec. 11, 1956 2,852,331 Youse Sept. 16, 1958 2,940,812 Denyer et a1 June 14, 1960 2,997,362 Baumann Aug. 22, 1961 

1. A PROCESS WHICH COMPRISES DYEING WOOL WITH DYESTUFFS CONTAINING AT LEAST 2 HO3S-GROUPS IN THE PRESENCE OF A COMPOUND OF THE FORMULA 